The effects of electrode materials on the switching behaviour of the amorphous semiconductors Si12Ge10As30Te48

The switching behaviour of the amorphous chalcogenide alloy Si₁₂Ge₁₀As₃₀Te₄₈ has been systematically investigated using silver, indium, aluminum, and graphite for electrodes. The experimental results show that the stability in both the threshold voltage for the onset of switching action, and the holding current required to maintain the conducting state, depends strongly on electrode materials. The switching mechanisms related to the electrical and thermal properties of various electrode materials are discussed, and experimental evidence of the deteriorating effect of some electrode materials is given.     

Structural investigation of amorphous and liquid Ge0.175Te0.825 by neutron scattering

The angular distribution of intensities of 1.003 Å neutrons scattered by an alloy of Ge_0.175Te_0.825 both in the amorphous and in the liquid state have been measured. The bulk amorphous sample, prepared by water quenching of the melt, has been examined at room temperature and just above the crystallization temperature T_x. The liquid sample has been examined at 400, 600 and 800°C. The analysis of the structure factors obtained from the corrected and scaled intensities indicates that the structural features of the amorphous sample are similar to those which would be expected if it were possible to cool the alloy to room temperature, while maintaining it in the liquid state. The analysis of the radical distribution functions, from Fourier inversion of the structure factors, indicates that a change of the coordination number n₁ from 2.43 to 3.25 occurs in passing from the amorphous to the liquid state at 400°C. This result has been interpreted in terms of coordination models. In the liquid state, it has been found that a model with fourfold coordinated Ge and threefold coordinated Te is consistent with n₁=3.25. The internal consistency of this model for the liquid state allows us to make a reasonable choice between the possibility of a 3 or 4 fold coordination for Ge in the glass. We conclude that a model based on four-fold coordinated Ge and twofold coordinated Te seems an appropriate representation for the coordination of the amorphous material.     

Photoconductivity of oxychalcogenide glasses in the system As2Se3CdO

The photoconductivity of oxychalcogenide glasses in the system As₂Se₃CdO was investigated. When 2–3 mol % CdO was added, the photoresponse peak of the parent glass As₂Se₃ in the vicinity of 740 nm became broader and a little weaker. The addition of more than about 4 mol % CdO brought about a sharp and strong peak at 720 nm and a broad peak at 860 nm. X-ray diffraction and electron microscopic observations revealed the presence of crystalline CdSe in the glass matrix, indicating that the reaction As₂Se₃ + 3CdO → As₂O₃ + 3CdSe took place in the melting process of these glasses. Tempeature and light intensity dependences of the photocurrent lead to the conclusion that the above spectral photoresponse is greatly affected by the presence of the dispersed crystalline CdSe.     

Investigation of recombination and trapping processes in 3As2Se32Sb2Se3 amorphous films by photoconductivity method

Photoconductivity experiment has been performed on high resistivity ($\text{π ? 10}{}^9\text{Ω-}\text{cm}$) 3As₂Se₃2Sb₂Se₃ amorphous films in the temperature range from 278°K to 308°K, as a function of light intensity, I₀. The results are that at intermediate light levels the photocurrent varies as I₀^0.7 and at high light levels the photocurrent is directly proportional to I₀. A simple recombination and trapping model is developed to interpret the observed photoconductivity data. From the temperature dependence of the photocurrent, an effective trap level located 0.3 eV below the band edge is deduced.     

Immiscibility and liquidus temperatures in the pseudobinary chalcogenide system PbSeGe1.5As0.5Se3

Electron microscopy studies of growth of microstructure or crystal size as a function of heat treatment temperature have been used to determine immiscibility and liquidus temperatures in the pseudobinary chalcogenide system PbSeGe_1.5As_0.5Se₃. The immiscibility dome was found to span nearly the entire pseudobinary composition region, in good agreement with the results of a previous heat capacity study of this system in the glass transition region.     

Electrical conductivity and photoconductivity of As2S3PbS glasses

Measurements of dc electrical conductivity and photoconductivity of various glassy compositions (x = 0.1?0.625) in (As₂S₃)_1?x(PbS)_x have been made. Experimental results of the temperature dependence of dc conductivity from room temperature to 200°C (which includes the glass transition temperature) are reported. All the compositions exhibit intrinsic conduction in the measured temperature range. Thermal activation energy, glass transition temperature and σ₀ for the compositions studied, were determined from the experimental data. The low value of $\text{σ}{}_0\text{(10?10}{}^{\mathrm{?2}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$) in these semiconducting glasses is attributed to the greater participation of localized states in the conduction process.In the measurements of photoconductivity, the variation of photocurrent with temperature, photon energy, light intensity and electric field is observed. The recombination model has been involved to explain the results of photoconductivity. Both electrical and photoconductivity data support the presence of higher density of localized states in the x = 0.1 composition than in others.     

Nuclear magnetic resonance studies of the glasses in the system Na2OB2O3SiO2

The ¹¹B NMR spectra have been used to study the structure of glasses in the system Na₂OB₂O₃SiO₂. The fraction of BO₄ units, and the fraction of BO₃ units with one or two nonbridging oxygens, are measured and analyzed according to a structural model. The results indicate that: (1) for a sodium oxide to boron oxide ratio of 0.5 or less, the Na⁺¹ ions are attracted primarily by the borate network; therefore, the ternary glasses can be viewed as binary sodium borate glasses diluted by SiO₂; (2) when the sodium oxide to boron oxide ratio exceeds 0.5, the additional Na₂O results in the formation of [BSi₄O₁₀]^?1 units at the expense of diborate and SiO₄ units. In this process, Na⁺¹ ions are still taken up only by the borate network. After all the available SiO₄ units are consumed to form [BSi₄O₁₀]^?1 units, additional Na⁺¹ ions are proportionally shared between the borate and silicate networks.     

ESR and optical absorption of Cu2+ in Na2OSiO2 glasses

ESR and optical absorption spectra of Cu²⁺ in xNa₂O(100?x)SiO₂ glasses were measured, where x ranges from 12 to 70 mol% Na₂O. This glass system was divided into three composition regions, 12 ? x ? 37, 37 ? x ? 55 and 55 ? x, from the composition dependence of the ligand field transition energy and spin hamiltonian parameters of Cu²⁺. Two boundary compositions (37 and 55 mol%) between the two adjacent regions agreed with the eutectics in the equilibrium phase diagram. Two types of Cu²⁺-complexes, with less basic ligands (HFS-1) and much more basic ones (HFS-2), were detected in ESR for ultra-high soda glasses (x ? 55). The distribution of the ESR parameters due to the fluctuation of ligand fields was negligible for HFS-2 compared with that for other glasses. The Cu²⁺ ion responsible for HFS-2 was considered to distribute in the microphase of orthosilicate. Imagawa's basicity, the covalency of the bondings between Cu²⁺ and ligands, was calculated by using Maki and McGarvey's analysis. The basicity of σ-type symmetry remained constant, irrespective of the glass composition, and the value was identical with those for other oxyanionic glasses. The π-type basicity was also constant for the glasses of x ? 55. Two different basicities, each corresponding to HFS-1 or 2, were obtained for the glasses of x ? 55. The value derived from HFS-1 was identical with those for x < 55 glasses, whereas that derived from HFS-2 suggested the formation of much more basic ligands.     

Phase separation in GeGeO2 glasses

De Neufville prepared homogeneous glasses ranging in composition from pure GeO₂ to GeO by quenching bulk samples from the melt and by vapor deposition. For compositions in the range of 10–20 mol % excess Ge dissolved in GeO₂, he found that phase separation into amorphous Ge rich and amorphous GeO₂ phases occurred. The results reported here on a 7.5 mol % excess Ge composition using differential scanning calorimetry have shown that a two-step phase separation mechanism is operative. A homogeneous GeGeO₂ glass phase separates at 450°C into amorphous GeO₂ and amorphous GeO. The GeO phase separates at 570°C into crystalline Ge and amorphous GeO₂. The heat measured at 570°C is equal to the sum of the heats of phase separation of GeO and crystallization of Ge. The amorphous GeO₂ crystallizes at 670°C with a heat of crystallization of 4.65 kcal/mol (± 0.5). Additional support for a two-step phase separation mechanism is provided by kinetic arguments based on the viscosity dependence on composition and on the structure of the amorphous GeO phase and its stability relative to the homogeneous GeGeO₂ glass.     

Infrared spectra and structure of superionic conducting glasses in the system AgIAg2OMoO3

Thin blown films of glasses with the mole ratio Ag₂O/MoO₃ = 1 in the system AgIAg₂OMoO₃ (or the pseudobinary system AgIAg₂MoO₄) show three absorption bands in the range 4000-200 cm^?1; 875 cm^?1 (w), 780 cm^?1 (s), and 320 cm^?1 (m, b), which are characteristic of tetrahedral MoO₄^2? ions. The glasses with the ratio Ag₂O/MoO₃ < 1 have two additional bands at 600 cm^?1 (w) and 450 cm^?1 (vw), which are characteristic of condensed ions of MoO₄ tetrahedra, probably Mo₂ O₇^2? ions. These glasses are thus composed of Ag⁺, I^?, MoO₄^2?, and probably Mo₂O₇^2? ions, and classified as “ionic” glasses containing one type of cations. The presence of partial covalency in the Ag⁺… ^?OMo link and the influence of ion exchange of Ag⁺ with K⁺ on IR spectra are discussed. The molar volume of the glasses with the ratio Ag₂O/MoO₃ = 1 is primarily determined by a fairly dense packing of the constituent anions, I^? and MoO₄^2?.     

Mössbauer study of the amorphous Pd70Fe10Si20 alloy upon transition to the crystalline state

Foils of the amorphous alloy Pd₇₀Fe₁₀Si₂₀ were investigated after isothermal heating at the temperature range 350–450°C with a heating period from 15 min to 4 h. At 350°C no changes were observed in the shape of the Mössbauer spectra. At 400°C and at 450°C up to 30 min only the parameters of Mössbauer spectra consisting of two quadrupole doublets corresponding to palladium and silicon vicinities of iron atoms were changed. After further heating at 450°C crystalline phases of Pd₃Fe and Fe₃Si appeared on the Mössbauer spectra.     

Small polaron conduction in V2O5P2O5 glasses

Dc conductivity measurements have been made between 90 and 520 K on three bulk samples of V₂O₅P₂O₅ glass. Heat treatment is found to result in a reduction of the activation energy at a given temperature and this is most noticeable at low temperatures. The behaviour at low temperatures can be described using Mott's variable range hopping arguments, and at high temperatures by non-adiabatic small polaron hopping between nearest neighbours. At intermediate temperatures a simple model is used in which excitations by optical and acoustic phonons are considered to make independent contributions to the jump frequency. Mott's theory is extended to the polaron case for $\text{T>}\text{1}\text{4}\text{?}$ and is shown to be in good agreement with results. Values for $\text{r}{}_{\mathrm{<mtext>p</mtext>}}\text{(～2.8}\text{A}\text{?}\text{)}$ the polaron radius and $\text{α(～3.5}\text{A}\text{?}{}^{\mathrm{?1}}\text{)}$ the electron decay constant are shown to be consistent with the model for small polarons. A method is suggested for obtaining α and N(E_F) from the ac conductivity and the slope of 1nσ versus $\text{1}\text{T}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}$ at low temperatures. Values of N(E) are obtained which correlate with those obtained by the previous analysis. This implies that the disorder energy separating adjacent sites Δ₀ is large (～0.4 eV) in these materials.     

A thermodynamic and kinetic investigation of amorphous (1−x)As2Se3 · xSb2Se3 alloys

The heats of formation of amorphous (1?x)As₂Se₃ · xSb₂Se₃ (x = 0 to 0.4) referred to crystalline As₂Se₃ and Sb₂Se₃ were measured by liquid metal solution calorimetry. The values of heats of formation of amorphous (1?x)As₂Se₃ · xSb₂Se₃ decreased from 1.39 ± 0.03 kcal · (g-at)^?1 at x = 0 to 1.27 ± 0.04 kcal · (g-at)^?1 at x = 0.4.The glass transition temperature and the temperatures of the maximum rates of crystallization and fusion were measured by differential scanning calorimetry. The glass transition temperature increased and the temperatures of the maximum rates of crystallization and fusion decreased with increasing Sb₂Se₃ content.The relaxation process in amorphous (1?x)As₂Se₃ · xSb₂Se (x = 0.3) was investigated by measuring changes in microhardness, small-angle X-ray scattering and heat capacity with time of annealing at several temperatures ranging from room temperature to 413 K. With increasing annealing time the microhardness, the height and the temperature of the glass transition peak increased whereas the intensity of small-angle X-ray scattering decreased. These changes reflect relaxation towards a more stable structure of smaller molecular mobility. The changes in the enthalpy with annealing time and the activation energy spectra for relaxation were derived from the heat capacity data. The effects of temperature and time of annealing on the various properties are explained in terms of structural changes and relaxation kinetics.     

EPR study of crystalline and vitreous forms of the Li2OAl2O3SiO2 system

The epr spectra of V⁴⁺ and radiation centres have been studied in β-eucryptite (LiAlSiO₄), β-, γ-spodumene (LiAlSi₂O₆) and in glasses prepared by the fusion of the single crystals. It is shown that the electronic structures of the vitreous state in the Li₂OAl₂O₃SiO₂ system and that of the crystalline forms differ considerably. The change of the electronic structure on crystallization is not direct, but is realized through the intermediate state whose electronic structure differs from that of glasses and crystals.     

Composition dependence of the refractive index and its photo-induced variation in the binary glass systems: Ge1−xSex and As1−xSex

The composition dependence of the refractive index and its photo-induced variation have been calculated for the Ge_1?xSe_x and As_1?xSe_x binary glass systems, using the random network model. It is found that the refractive index has a minimum in Ge_1?xSe_x at x = 0.8, while it shows a monotomic increase with increasing As content in As_1?xSe_x glasses. The refractive index of the Ge_1?xSe_x system decreases with illumination and the variation Δn of GeSe₂ is ?0.0316, while the refractive index of the As_1?xSe_x system increases with illumination and the variation of As₂Se₃ is 0.01. These results are in agreement with the experimental results reported by several workers.     

Glass formation in the systems (K or Cs)2O(Nb or Ta)2O5Al2O3

The glass-forming ability of melts in the systems K₂O(Nb and/or Ta)₂O₅Al₂O₃ as well as those in which K₂O was replaced with Li₂O, Na₂O, Cs₂O, BaO or PbO was investigated. Some melts in the systems (K or Cs)₂O(Nb and/or Ta)₂O₅Al₂O₃ could be made into glasses by cooling, yielding practically useful amounts. The structures of these glasses were discussed on the basis of their infrared spectroscopic and X-ray emission spectroscopic analyses.     

Short range antiferromagnetic ordering in vitreous Fe2O3P2O5

An outline is given of the theory of neutron magnetic scattering from amorphous materials, and data are presented for vitreous 0.79 Fe₂O₃ · P₂O₅. The magnetic correlation function shows that at low temperatures the glass exhibits short-range antiferromagnetic ordering with Fe³⁺?Fe³⁺ interionic distances similar to those found in crystalline FePO₄. The neutron data are not consistent with a previous suggestion that the material is microcrystalline.     

11B and 27Al NMR studies of glasses in the system Na2OB2O3Al2O3 (“NABAL”)

¹¹B and ²⁷Al nuclear magnetic resonances (NMR) in glasses of the NABAL system Na₂OB₂O₃Al₂O₃ have been studied as a function of composition. From the boron data, the fraction of four-coordinated BO₄ units has been determined via computer analysis of the NMR spectra; the method is similar to that employed previously for binary and other ternary borate glasses. The ²⁷Al NMR indicates no abrupt change in the average aluminum environment. Certain linear relationships have been found which yield detailed information on the competing processes of BO₃, BO₄ and AlO₄ formation, and the formation of triclusters consisting of three tetrahedra having one oxygen in common. Furthermore, it is concluded that the oxygen available for the formation of various aluminum-containing species is a function of the soda concentration only and that the conversion to AlO₄ is favored as compared with BO₄.     

Ab initio calculation on the (Si2O7)6− bitetrahedra

The total energy surface of the (Si₂O₇)^6? ion is calculated from the bend and torsion angles in the SiOSi axis. The results are discussed and compared with the experimental data. The ab initio calculation of (SiO₄)^4?, as well as the calculation of the charge distributions for all species were made and discussed.     

Brillouin scattering measurements of attenuation and velocity of hypersounds in SiO2B2O3 glasses

Measurements of hypersound wave velocity and attenuation (20–30 GHz) were made at room temperature by Brillouin scattering in SiO₂O₂O₃ glasses. The attenuation shows a maximum with composition. An explanation of this maximum is given in relation to the glass structure. It is thought that this maximum may be due to a coupling effect of hypersounds with structural relaxational process involving SiSi and SiOB bonds.